Triazinyl cyanoalkyl sulphides



Patented Sept. 15, 1942 UNITED STATES PATENT OFFICE azsassr TBIAZINYLCYANOALKYL SUIPHIDES Gaetano F. DAlello and James W. Underwood,Pittsiield, Mass, assignon to General Electric Company, a corporation ofNew York No Drawing. Application June 27, 1941, Serial No. 400,150 V 11Claims.

This invention relates to new chemical compounds and more particularlyto triazine derivatives. The invention especially is concerned with theproduction of new and useful symmetrical triazinyl (s-triazinyl)cyanoalkyl sulphides.

The triazinyl cyanoalkyl sulphides of this invention may be representedgraphically'by the following general formula: I

In the above formula 11. represents an integer and is at least 1 and notmore than 3, a: is an integer and is at least 1 and not more than 2, andR represents a member of the class consisting of hydrogen and monovalenthydrocarbon and halohydrocarbon radicals, numerous examples of whichhereafter are given. Since n: represents an integer which is 1 or '2, itwill be seen that the linkage of the cyanoalkyl group to the sulphuratom in all cases will be alpha or beta to the cyano group. It also willbe observed that linkage of the triazinyl grouping to the sulphur atomis through a carbon atom. From a consideration of the formula it furtherwillbe seen that when n is 3 there will be no amino (--NI-IR) groupsattached to the triazine nucleus.

Illustrative examples of nionovalent hydrocarbon radicals that R in theabove formula may represent are aliphatic (e. g., methyl, ethyl, propyl,isopropyl, allyl,.butyl, secondary butyl, isobutyl, butenyl, amyl,isoamyl, hexyl, etc.), including cycloaliphatic (e. g., cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc); aryl (e. g.,phenyl, diphenyl, naphthyl, etc); alkaryl (e. g., tolyl, xylyl,ethylphenyl, propylphenyl, isopropylphenyl, etc.); aralkyl (e. g.,.benzyl, phenylethyl, phenylpropyl, etc.);

and their homologues, as well as those groups with one or more of theirhydrogen atoms substituted by, for example, a halogen. Specific examplesof halogeno-substituted hydrocarbon radicals are chlormethyl,chiorcyclohexyl, chlorphenyl, dichlorphenyl, ethyl chlorphenyl,phenylhydrazine, etc.. derivatives of the individual triazinylcyanoalkyl-sulphide. These new organic sulphides are especially valuableas reactants in (01. zoo-24 a) I products are more fullydescribed andclaimed in our copendlng application Serial No. 400,149, filedconcurrently herewith and assigned to the same assignee as the presentinvention. In our copending application Serial No. 441,546, filed May 2,1942, which application is a continuationin-part of the presentapplication and of application Serlal No. 400,149, we have more fullydescribed and have specifically claimed composi tions of mattercomprising the product of reaction of ingredients comprising an aldehydeand acompound corresponding to the general'formula,

where n represents an integer and is at least 1 and not more than 2, Itrepresents a member of the class consisting of hydrogen and monovalenthydrocarbon and'halo-hydrocarbon radicals, and

-X represents a halogen atom. The aldehydeaddition products of our newtriazinyl'cyanoalkyl sulphides also may be compounded with rubber, bothnatural'and synthetic, to modify the properties of the rubber.

Various methods may be employed to produce the chemical compounds ofthis invention. We

prefer to prepare them by efiecting reaction between a mercaptos-triazine and a mono-halogenated alkyl cyanide (mono-halogenatedcyanoalkane) in the presence of a hydrohalide acc'eptor. Illustrativeexamples of mercapto s-triazines'that may be used, depending upon theparticular s-triazinyl cyanoalkyl sulphide desired, are: a

4,6-diamino 2-mercapto s-triazine fi-amino 2,4-dimercapto s-triazine.

(ii-amino 4,6'-dimercapto s-triazine) 2,4,6-trimercapto s-triazine4,6-di-(methvlamino) Z-mercapto s-triazine 4,6-diani1ino 2-mercaptos-triazine 4,6-di-(cyclohexylamino) Z-mercapto s-triazine 4,6-ditoluido2-mercapto s-triazine 4-benzylamino B-methylamino z-mercapto s-triazine,which also may be named 4-methylamino G-benzylamino Z-mercaptos-triazine Typical examples of mono-halogenated alkyl cyanides that maybe employed, depending upon the particular end-product sought, are:

Alpha-chloro alpha-ethyl beta-phenvl butyronitrile Illustrative examplesof hydrohalide acceptors that may be used are the inorganic bases, e.g., the alkali-metal hydroxides (sodium hydroxide, potassium hydroxide,etc.), calcium hydroxide, barium hydroxide, ammonium hydroxide, etc.,the carbonates of such bases, and the organic bases, e. g., tertiaryamines such, for instance, as trlmethyl amine, tributyl amine, dimethylaniline, pyridine, quinoline, etc., quaternary ammonium bases (e. g.,tetramethyl ammonium hydroxide, etc.), and the like. Preferably thehydrohalide acceptor is one that will react with the mercapto s-triazineto form a water-soluble salt. Examples of such preferred acceptors aresodium and potassium hydroxides.

The reaction between the mercapto s-triazine and the mono-halogenatedalkyl cyanide (monohalogenated cyano-alkane) may be carried out in anysuitable manner, but preferably is eflected in the presence of asuitable solvent or mixture of solvents. Although various solvents orsolvent mixtures may be employed we prefer, for economic reasons andbecause of their eminent suitability, to use water or a mixture of waterand alcohol. The reaction may be carried out under a variety oftemperature and pressure conditions, for instance at normal or atelevated temperatures and at atmospheric, sub-atmospheric orsuper-atmospheric pressures. I

The above reaction may be. represented by the following generalequation:

N v -(NH l)l- 1|(hydrohalide 0 C- I acceptor) IE, Ilq -(SH)u+ (CR:)r-CNJ fi I N V C/ |(NHR)a- I I! {scR, .cN].+ (salt of aggplggrohalide In theabove equation X represents halogen and R, a and a: have the samemeanings as given above with reference to the general formula I for thes-trlazinyl cyanoalkyl sulphides of this invention.

The chemical compounds of this invention also may be prepared byeffecting reaction between a halogenated s-trlazineand a mono-mercaptoalkyl cyanide (mono-mercapto cyano-alkane) in the presence of ahydrohalide acceptor. This reaction may be carried out by any suitableThe other conditions of reaction may bethe same as described above withreference to the first-mentioned method of preparation. C/

. means but preferably is effected in the presence of an anhydroussolvent, e. g., alcohol.

Illustrative examplesothalimteds-tliallnes that may be used, dependmgupon the desired end-product, are:

diamino s-trlazine) 6-iodo 2,4-diamino s-triazine 4,6-dichloro 2-amiuos-triaxine 2,4,6-trichloro s-triasine 6-chloro 2,4-di-(methylamino)s-triazine 4-chloro 2-amino B-anilino a-tl'iazine 2-chloro 4-toluidoB-ethylamino s-trlazine 4,6-dibromo 2-cyelohexylamlno s-triaxine 6-iodo2,4-di- (benaylamino) s-trlaaine Illustrative examples of mono-mercaptoalkyl cyanides that may be used,

(1 particular product dwired, are:

Mercapto acetonitrlle Alpha-mercapto butyronitrlle upon theBeta-mercapto alpha-phmyl p roplonitrile Beta-mercapto beta-chlorphenyltrile Beta-mercapto beta-phmvl mnltrile Beta-mercapto alpha-benaylalpha-methyl bu- -phenyl alpha-ethyl butyronitrile Beta-mercapto a1tyronitrile Alpha-mercapto beta-tolyl butyronitrlle Alpha-mercaptobeta-benzyl butyronitrile The hydrohalideacceptormaybethesameasdescribed above with reference to the first-named method of preparingthe of this invention.

The general reaction for this alternative method of preparingillustrated by the followin equation:

' v ama) -c c- I II X.

m was reams lnthisequationmxaandzhavetbesame meanings as definedhereinbetore with reference to Formula Iand EquationII.

A more specific illustration of how these new compounds may be p paredis below with reference to the preparation of 4.6-diamino s-triazinyl-2cyanomethyl sulphide, the formula for which is III The above componentswere mixed with 21000 and 2,000 parts of alcohol. Theto react at roomtemperafter which it was heated for oln-newchuniealoompoundsisr 1 houron a boiling water bath. The mixture was cooled. The product wasfiltered of! and washed well with hot water. A yield of 161 parts of4,6-diamino s-triazinyl 2 cyanomethyl sulphide was obtained. No attemptwas made to recover any more from the mother liquor.

As it will be readily understood by those skilled in the art, when it isdesired to produce compounds containing a single mono-amino trlazinylgrouping and two cyanoalkyl sulphide groupings or compounds containing atriazinyl grouping and three cyanoalkyl sulphide groupings, then thestarting reactants and Proportions of reactants are chosen so as toyieldthe desired products in accordance with methods such as above given byway of illustration.

From the foregoing description it will be seen that the presentinvention provides new and useful s-triazinvl cyanoalkyl sulphides.examples of which are s-triazinyl tri-(cyanomethyl sulphide),s-triazinyl tri-(cyanoethyl sulphide), the monoamino (NHR) s-triazinyldi-(cyanomethyl sulphides) the monoamino (NHR) s-triazinyl di-(cyanoethyl sulphides), the diamino (-NHR) 2] s-triazinylmono-(cyanomethyl sulphides) and the diamino [(-NHRM] s-triazinylmono-(cyanoethyl sulphides). Other and more specific examples of thesenew compounds are shown below:

C -CHi-CHz-ON s-Triazinyl-Z, 4, 6 tri-(beta-cyanoethyl sulphide) HzN-CCSCH:N

11 I C -GHz-CN B-amlno s-triaziuyl-2,4 dl-(cyanomethyl sulphide) NHaN-(f HzN-C C H2C N N\ I /N C NIH-C 11 v fi-amino i-anilinos-triazinyl-Z cyanomethyl sulphide XI N HzN-C C--SH-CN l l O NH-CaHno-amino 4-eniiino s-triazinyl-2 cyano-pheuylmethyl sulphide NHCeH4---CH;15 fi-methylamino 'i-toluido s-triazinyl-2 beta=cyanoethyl sulphide N HN-C C-S-CH-CII xnr 1 r a N N CN NH: 4,6-diamino s-triazinyl-2alpha-cyanoethyl sulphide N CzHs CEa-HN-C CS--CHCHGN -XIV I II N CeHnNIP-CH;

4,6-di-(methylamino) s-triazinyl-2 beta-(alpha-cyclohexyl cyanobutyl)sulphide N QHr-CeH-i CHr-CeH4NH-C C-S-CHCH:CN XV I ll /N g NHCeHr-CH; v4, -toluido s-triazinyl-2 beta-(gamma-pheuyl eyanopropyl) v sulphide 40N CeHu-HNC C-S-CH-CHr-CH; XVI I l ON l 0 11 4,6-di-(cyclohexylamino)s-triazinyl-2 alpha-cyanopropyl sulphide N z u CmHvHN-(f (fi-S-JJH-CN NN XVII I B-OH-CN 2H; 6-naphthylamino 2-trlazinyl-2,4di-(alpha-cyanopropyl sulphide) N clrn-rm-o O-S-CH-ON N QHQCX XVIIILOB-ON cimol d-ethylamino s-triazinyl-2,4 di-(cyanomhlorphenylmethylsulphide) GEE; N 00 15 5 i v a, r--

NC-(|JHCES-(|l GISCH- H CN C H N H XIX a a a s C CeHt CH H-CNe-triazinyl-2,4,6 trl-[beta-(alpha-phenyl cyauobutyl) sulphide] In amanner similar to that described above with particular reference to theproduction of s-triazinyl cyanomethyl and cyanoethyl sulwhere n is an-integer and is at 1east,1 and not more 3, :c is an integer and is atleast 1 and not more than 2, and R is a member or the class consisting'of hydrogen and monovaient hydrocarbon and halo-hydrocarbon radicals.

2. Chemical compounds as in claim 1 wherein R represents hydrogen.

3. Chemical compounds as in claim 1 wherein R represents hydrogen and a:is 1.

4. Symmetrical triazinyl-2,4,6 trI-(cyanomethyl sulphide).

5. A- monoamino s-triazinyl di-(cyanomethyl sulphide) 6. G-aminosulphide).

'7. 'A dlamino 's-trlazinvl cyanomethyl sulphide.

8. 4,6-diamino s-triazinyl-2 cyanomethyl sulphide.

9. .The method of preparing chemical compounds corresponding to thegeneral formula s-triaziny1-2,4 di-(cyanomethyi where'n isan in r and isat least i and not more thant, a: is an integer and is at least 1 andnot more than 2, and R is a member or the class consisting of hydrogenand mcncvalent hydrocarbon and halo-hydrocarbon radicals. said methodcomprising effecting reaction, in the presence of a hydrohalideacceptor, between (i) a mercapto s-triasine corresponding to the generalformula N f-r -l where n and B have the meanings above given, and (2)mono-halogenated alkyi cyanide corresponding to the general formula 1where x represents halogen and R, n and a: have ammo F. DALELI 0. JAMESw. UNDERWOOD.

